Zwitterionic functionalized polymers as deflocculants in water based drilling fluids

ABSTRACT

A water soluble polymer which is characterized by the formula: ##STR1## wherein x is 50 mole percent or 662/3 mole percent or 75 mole percent and y+z is 50 mole percent, when x is 50 mole percent, y+z is 331/3 mole percent, when x is 662/3 mole percent, and y+z is 25 mole percent, when x is 75 mole percent, wherein the molar ratio of y to z is about 100:1 to 1:100, and M +  is hydrogen or a metal cation selected from the group consisting of lead, aluminum, iron and Groups IA, IIA, IB and IIB of the Periodic Table of Elements and the level of sulfonation based upon the styrene monomer is about 75 to about 100 mole percent.

FIELD OF THE INVENTION

The present invention details the synthesis, rheology, drilling fluidproperties of a novel low molecular weight, water soluble terpolymercontaining nonionic, sulfonate (ionic), and zwitterionic (imide-type)functionalities chemically attached to the polymer chain backbone. Theinitial starting copolymer is composed of alternating styrene and maleicanhydride units. Molecular weight is typically less than about 10,000g/mole. This material can be formed via conventional free radicalpolymerization procedures. This copolymer can subsequently be fullysulfonated via well-known procedures. This procedure is able to fullysulfonates the styrene units leaving the maleic anhydride moietiescapable of further reactions. Subsequently, the maleic anhydridemoieties are used for incorporation of zwitterionic functionalities ontothe chain backbone. These terpolymers are found to be very effectivedeflocculents in conventional water based drilling fluids. Thezwitterionic functionality is chemically bound to the polymer viaimidization-type chemistry.

BACKGROUND OF THE INVENTION

Oil-based drilling muds have received considerably attention and enjoyedincreasing utilization for drilling oil and gas wells because thesefluids possess stable rheological and filtration properties at elevatedtemperatures. The oil-based fluid enhances borehole stability, corrosioncontrol, and lubricity. The so-called relaxed filtration muds allowsdrilling to occur at a relatively rapid rate with these fluids(particularly in shale type formation). In addition, the introduction oflow-aromatic mineral seal oils as a replacement for the moreconventional diesel oils has also reduced the environmental concernsassociated with accidental spills.

Wider use of oil-based fluids, however, is being reduced by certainfactors which include, among other factors, the various environmentalrestraints placed on them. In offshore and inland waters, oil muds maybe used but can not be discharged into the water regardless of the oiltype used in the operation. Cuttings may be discharged provided theyhave been thoroughly clean of oil; however, cuttings-wash techniques areexpensive; sometimes ineffective and can lead to expensive seabedcleanup operations.

Perricone, et. al. have extensively and eloquently reviewed the subjectof high temperature filtration control additives (SPE DrillingEngineering, 358, October, 1986). Pertinent excerpts from this revieware noted below.

It has been found that oil muds should be avoided in area prone tolost-circulation problems if the mud density must be maintained near thefracture pressure of the exposed formation. In directional holes largerthan 12 in. (30 cm) in diameter in which a fast penetration rate isexpected, he recommends not using the oil mud if other options exist.

The industry must have available other fluids systems if it is to drillthe deep, expensive wells of the future. No one product is necessarilythe answer to improved fluids. A total-systems concept consisting ofseveral products must be integrated to meet the changing demands on thefluid during the course of drilling the well. These systems will requirea series of new materials, each with a particular function, to be usedwhen needed.

Researchers have look continuously at improving the thermal stability ofwater-based muds. In 1973, U.S. Pat. No. 3,764,530 was granted thatcovered the application of a low-molecular-weight sodium polyacrylatefor stabilizing the rheology of aqueous muds at elevated temperatures.Earlier that year, Perricone and Young were granted a U.S. Pat. No.3,730,900 covering the use of a sulfonated styrene/maleic anhydridecopolymer for stabilizing the rheology of water-based muds at hightemperatures. The primary advantage of the latter copolymer was itsincreased resistance to cement and calcium ion contaminations.

Improved mechanical equipment and greater emphasis on solids removalhave contributed to better fluid systems. A reduction in the quantity ofbentonite added to a system has aided in the control of high-temperatureflow properties.

Filtration control of water-based system, particularly above 300° F.(149° C.), has received the attention of many investigators whoattempted to develop new products to improve control of this property.The natural polymers commonly used as filtration-control agents are noteffective at the higher bottomhole temperatures (BHT's). The starchesand cellulose derivatives are thermally degraded by oxidation andhydrolysis reaction, producing lower-molecular-weight by-products thatcause a substantial loss of viscosity and filtration-controleffectiveness. The rate of degradation depends on the fluid, dissolvedoxygen, pH of the mud system, and time of exposure to elevatedtemperature. It has been taught that starches not be used routinelyabove 225° F. (107° C.) nor carboxymethylcellulose-based products above300° C. (149° C.).

Lignitic products are used for filtration control in high densitywater-based muds. Upon neutralization with caustic soda, ligniteproduces a water-soluble salt with some remaining caustic-insolubleresidue. This sodium salt is quite sensitive to electrolytes and canform insoluble calcium carboxylate products in the presence of solublecalcium compounds. Improved resistance to electrolytes can be obtainedby the use of higher mud alkalinities or sulfonation of the lignite. In1976, a combination dispersing filtration-control agent containing asulfonated lignite and a phenol-formaldehyde resin in U.S. Pat. No.3,950,140. This product was reported to be superior in performance andless sensitive to calcium and other electrolytes. Although lignite isrecognized as more resistant to thermal degradation of lignite doesoccur, producing intermediate acid compounds and ultimately aliphaticand aryl carboxylic acids.

Treatment level for such lignite products may vary from 1 to more than20 lbm/bbl (2.85 to 57 kg/m³). Over treatment may lead to increase inviscosity and rate of gelation of the mud, which can be controlled onlyby dilution with water.

The importance of and need for improved filtration-control polymers isindicated by the number of U.S. Pat. Nos. (3,025,234; 2,775,557;3,072,596; and 4,357,245) granted over the years in an effort to produceimproved products for drilling muds. Derivatives of hydrolyzedpolyacrylamide and acrylic acid are essentially the only polymers to beused commercially in drilling muds for filtration control. Because thesepolymers lack tolerance toward electrolyte contamination, they havelimited application.

Various criteria have also been noted by Perricone, et. al. on thespecific characteristics required in the preparation of an effective,thermally stable deflocculant. The following list details some of thesedesirable characteristics:

1. The polymer should be water-soluble and anionic.

2. It should be thermally stable and resistant to alkaline hydrolysis.

3. It should be an effective filtration-control additive in the presenceof electrolytes.

4. Its' molecular weight should be sufficient to control filtration butnot so high as to effect the rheology of the system drastically or to besusceptible to shear degradation.

5. It must be cost-effective.

6. It should be easily handled and stored at the rig site.

7. It should be environmentally acceptable.

Perricone et. al. have detailed the properties of two synthetic highmolecular weight vinyl sulfonate copolymers and their utilization incontrolling high temperature filtration properties in water-baseddrilling muds. These copolymers are more effective at high temperaturesbecause they do not depolymerize in oxidative or hydrolytic conditions.These materials do not form unsoluble salts with the addition of solubleelectrolytes.

It should be noted in this regard that the use of hydrophobic groups onwater soluble polymers to enhance the rheological properties of waterbased fluids has been described. One approach to provide polyacrylamidebased systems containing hydrophobic groups is described by Bock, et.al., U.S. Pat. No. 4,520,182 and 4,528,348. Water soluble acrylamidecopolymers containing a small amount of oil soluble or hydrophobicalkylacrylamide groups were found to impart efficient viscosification toaqueous fluids. Landoll, U.S. Pat. No. 4,304,902, described copolymersof ethylene oxide with long chain epoxides which also requiredrelatively large polymer concentration (approximately 1%) for thickeningwater and required surfactant for solubility due to irregularities inthe polymerization. In a related case, U.S. Pat. No. 4,428,277, modifiednonionic cellulose ether polymers are described. Although these polymersshow enhanced viscosification relative to polymers containinghydrophobic groups, the viscosification efficiency was very low,requiring 2 to 3 weight percent polymer to provide an enhancement. Theuse of surfactants to enable solubility and, in turn, viscosification,by a water soluble polymer containing hydrophobic groups is described byEvani, U.S. Pat. No. 4,432,881. The hydrophobic groups claimed areattached to the polymer via an acrylate linkage which is known to havepoor hydrolytic stability. In addition, the need for a surfactant toachieve solubility and thickening efficiency should make such a systemvery salt sensitive, as well as very sensitive to small changes insurfactant and polymer concentrations. Emmons, et. al., U.S. Pat. No.4,395,524, teaches acrylamide copolymers as thickeners for aqueoussystems. While these polymers possess hydrophobic groups they areprepared using alcohol containing solvent which are known chain transferagents. The resulting polymers have rather low molecular weights and,thus, relatively high polymer concentrations are required to achievereasonable viscosification of water based fluids.

SUMMARY OF THE INVENTION

The present invention relates to the synthesis of a family of watersoluble polymers which when dissolved into a water based drilling fluidimparts improved deflocculation characteristics to the mud. Typically,the deflocculents are relatively low molecular weight polymers composedof styrene sulfonate (sodium salt) monomer, maleic anhydride (either asthe anhydride and/or the diacid) and a zwitterionic functionalizedmaleic anhydride. Typically the molar ratio of styrene sulfonate unitsto total maleic anhydride units is 3:1, 2:1 or 1:1. The level of alkylfunctionization of the maleic anhydride units is about 0.1 to about 100mole%, more preferably about 10 to about 100 mole%, and most preferably75 to 100 mole%. It should be noted that the molar ratio of sulfonate tozwitterionic units are not necessarily equivalent, since thedeflocculation properties of these water soluble polymers can becontrolled via changes in the said ratio.

The present invention relates to a water soluble terpolymer for use indrilling fluids, wherein the water soluble polymer is characterized bythe formula: ##STR2## wherein x is 50 mole percent or 66 2/3 molepercent or 75 mole percent and y+z is 50 mole percent, when x is 50 molepercent, y+z is 33 1/3 mole percent, when x is 66 2/3 mole percent, andy+z is 25 mole percent, when x is 75 mole percent, wherein the molarratio of y to z is about 100:1 to 1:100, more preferably, about 2:1 to1:2 and most preferably about 1.1:1.0 to 1.0:1.1 and M⁺ is hydrogen or ametal cation selected from the group consisting of lead, aluminum, ironand Groups IA, IIA, IB and IIB of the Periodic Table of Elements and thelevel of sulfonation based upon the styrene monomer is about 75 to about100 mole percent, more preferably about 80 to about 99.9 mole percent,and most preferably about 85 to about 99 mole percent.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates viscosity-temperature profiles of a high temperaturewater based mud containing no deflocculants.

FIG. 2 illustrates viscosity-temperature profiles of a high temperaturemud containing a deflocculant (Example 2) at a concentration of 1lb/bbl.

GENERAL DESCRIPTION

The present invention describes a new class of viscosification agentsfor water-based drilling muds which are used during operation of gas andoil wells, wherein these viscosification agents are terpolymers ofsodium styrene sulfonate/maleic anhydride/zwitterionic functionalizedmaleic anhydride. The water-based drilling muds of the instant inventionminimally comprise, but can also include other additives; an organicliquid such as an oil, fresh water or salt water, an emulsifier, awetting agent, a weighting material and the terpolymer. In general, thewater-based drilling mud has a specific gravity of about 7 pounds pergallon to about 20 pounds per gallon, more preferably about 12 to about16. A typical water-based drilling mud, as envisioned by the instantinvention, comprises about 5 to about 15 lb/bbl of a prehydrated gel, 1to about 30 lb/bbl of filtration control additives and weightingmaterial (barium sulfate or barite) necessary to give the desired muddensity; 5 to about 20 lb/bbl. of seasalt, 2 to about 100 lb/bbl ofstimulated drilling solids and caustic to adjust pH as desired.

Typical, but non-limiting examples of suitable emulsifiers which can bereadily employed are magnesium or calcium soaps of fatty acids.

Typical, but non-limiting examples of a suitable wetting agent which canbe readily employed is an alkylaryl sulfonate.

Typical, but non-limiting examples of a weighting material which can bereadily employed is barite or a barium sulfate which may optionally besurface-treated with other cations, such as calcium.

The instant invention describes a new class of water soluble polymerswhich impart improved deflocculation characteristics to water baseddrilling fluids. Typically, these polymers are formed by a free radicalcopolymerization process in a polar solvent system containing styreneand maleic anhydride monomers. The resultant copolymer contains styreneand maleic anhydride monomer units typically in a molar ratio of 3:1,2:1, or 1:1 depending on the initial polymerization conditions.Subsequently, these copolymers are sulfonated in order to form metalneutralized styrene sulfonate-maleic anhydride copolymers. The level ofsulfonation (based on styrene monomer content) is about 75 to 100 molepercent, more preferably about 85 to 100 mole percent, and mostpreferably 90 to 100 mole percent. The counterion of the sulfonate groupis an amine or a metal cation selected from the group consisting ofaluminum, iron, lead, Groups IA, IIA, IB and IIB of the Periodic Tableof Elements.

Subsequently, these sulfonate containing polymers are furtherfunctionalized in order to incorporate hydrophobically-associatinggroups into the polymer chain structure. The level of zwitterionicfunctionalization (based on maleic anhydride content) is about 0.1 toabout 100 mole%, more preferably 10 to about 100 mole%, and mostpreferably 75 to about 100 mole%.

The molecular weight, as derived from intrinsic viscosities, for thestarting copolymers of styrene/maleic anhydride is about 1×10² to about1×10⁵, more preferably about 1×10² to about 2×10⁴, and most preferablyabout 1×10³ to about 1×10⁴. The means for determining the molecularweights of the water soluble copolymers from the viscosity of solutionsof the copolymers comprises the initial isolation of the copolymers,purification and redissolving the copolymers in a solvent to givesolutions with known concentrations. The flow times of the solutions andthe pure solvent were measured in a standard Ubbelholde viscometer.Subsequently, the reduced viscosity is calculated through standardmethods utilizing these values. Extrapolation to zero polymerconcentration leads to the intrinsic viscosity of the polymer solution.The intrinsic viscosity is directly related to the molecular weightthrough the well known Mark-Houwink relationship. Gel permeationchromatography is also able to determine the detailed molecular weightdistribution of these polymers.

It should be pointed out that neither the mode of polymerization(solution, suspension, bulk or emulsion polymerization technique, andthe like), nor the initiation is critical, provided that the method orthe products of the initiation step does not inhibit production of thestyrene-maleic anhydride polymers or chemically modify the initialmolecular structure of reacting monomers.

The sulfonation of styrene monomers units incorporated into the polymerchain structure are well-known to those versed in the state of the art.Zwitterionic functionality are chemically bonded to the chain viaimidization-type chemistry. The preparation of conventional water-baseddrilling fluids are well-known to those versed in the state of the art.

The present invention relates to a water soluble terpolymer for use indrilling fluids, wherein the water soluble polymer is characterized bythe formula: ##STR3## wherein x is 50 mole percent or 662/3 mole percentor 75 mole percent and y+z is 50 mole percent, when x is 50 molepercent, y+z is 331/3 mole percent, when x is 662/3 mole percent, andy+z is 25 mole percent, when x is 75 mole percent, wherein the molarratio of y to z is about 100:1 to 1:100, more preferably, about 2:1 to1:2 and most preferably about 1.1:1.0 to 1.0:1.1 and M⁺ is hydrogen or ametal cation selected from the group consisting of lead, aluminum, ironand Groups IA, IIA, IB and IIB of the Periodic Table of Elements and thelevel of sulfonation based upon the styrene monomer is about 75 to about100 mole percent, more preferably about 80 to about 99.9 mole percent.

DETAILED DESCRIPTION OF THE INVENTION

The following examples will demonstrate the instant invention.

EXAMPLE 1

Sulfopropylation of 1-dimethylamino-2-amino-2-methylpropane (DMAAMP) wasformed as follows: Into a 500 ml round bottom flask equipped with an airdriven stirrer, a thermometer, and a nitrogen gas inlet, is 50.0 gDMAAMP and 250 ml acetone at room temperature. Propane sultone (52.5 g)is added slowly. The reaction is exothermic. The product is not solublein acetone and precipitates. The product is filtered, washed with excessacetone and dried at 30° C. for 48 hours. The yield was 75.5g of a whitesolid.

EXAMPLE 2

Into a round bottom flask equipped with a condenser, air driven stirrer,nitrogen gas inlet, and a thermometer, is added 100 g of the sulfonatedstyrene-co-maleic anhydride copolymer, 246.5 g of distilled water, 10.25sodium hydroxide, and 22.5 g of the sulfopropylated DMAAMP. The mixtureis agitated and a clear homogeneous solution is formed. The mixture isplaced in a pressure bottle and heated to 190° C. in an oil bath for 16hours. The mixture is cooled to room temperature and the functionalizedpolymer is isolated with a large excess of isopropyl alcohol. Thematerial is vacuum dried at 60° C. for 48 hours. Elemental analysis(1.75 weight percent nitrogen: 12.4 mole percent zwitterion content) wasused to determine the functionalization level.

EXAMPLE 3

The above water soluble zwitterion-containing polymer was dissolved infresh water and sodium chloride solutions. The rheological data clearlyshows that the addition of salt does not cause the anticipated decreasein viscosity, but in fact, an increase in performance is observed. Theunusual and useful behavior is due to the zwitterionic associationswhich becomes stronger in high brine environments.

EXAMPLE 4

This polymer was tested as a deflocculent in a standard high temperaturedrilling fluid. The composition of the fluid is described below (TableI):

TABLE I Standard High-Temperature Fluid Composition

    12 #/bbl prehydrated gel

    10.5 #/bbl seasalt

    Deflocculent, as indicated

    60 #/bbl RevDust (simulated drill solids)

    20.5 #/bbl Filtrex (filtration control material)

    2 #/bbl KemSeal (filtration control polymer)

    250 #/bbl Barite (for 13 ppg density)

    pH adjusted continuously to 10.0 with caustic, as needed

Note: #/bbl is approximated in the laboratory as gm/350 cc.

The challenge for any temperature-stable water-base drilling fluid is tomaintain controlled viscosity as the temperature increases. Clay-basedfluids traditionally undergo large viscosity increases with temperature,and the minimization of this increase is one of the objectives of thisinvention. The drilling fluid samples were all prepared at a density of13 ppg (1.56 specific gravity), equilibrated overnight for 16 hours at150° F., and then subsequently hot-roll-aged overnight for 16 hours at425° F., prior to testing.

The detailed rheological characteristics of the drilling fluid weremeasured with (FIG. 2) and without (FIG. 1) the above described polymer.A close examination of the data shows that the addition of thedeflocculent markedly improves the performance of the fluid over a broadtemperature range. This corresponds to a substantial enhancement in themud performance.

what is claimed is:
 1. A water soluble polymer which is characterized by the formula: ##STR4## wherein x is 50 mole percent of 662/3 mole percent or 75 mole percent and y+z is 50 mole percent, when x is 50 mole percent, y+z is 331/3 mole percent, when x is 662/3 mole percent, and y+z is 25 mole percent, when x is 75 mole percent, wherein the molar ratio of y to z is about 100:1 to 1:100, and M⁺ is hydrogen or a metal cation selected from the group consisting of lead, aluminum, iron and Groups IA, IIA, IB and IIB of the Periodic Table of Elements and the level of sulfonation based upon the styrene monomer is about 75 to about 100 mole percent.
 2. A water soluble terpolymer according to claim 1, wherein x is 50 mole percent and y+z is 50 mole percent. 